KR880701741A - New Supported Polymerization Catalyst - Google Patents

New Supported Polymerization Catalyst

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KR880701741A
KR880701741A KR1019880700511A KR880700511A KR880701741A KR 880701741 A KR880701741 A KR 880701741A KR 1019880700511 A KR1019880700511 A KR 1019880700511A KR 880700511 A KR880700511 A KR 880700511A KR 880701741 A KR880701741 A KR 880701741A
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bis
metallocene
titanium
cyclopentadienyl
olefin polymerization
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KR950010227B1 (en
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쥬니어 하워드 커티스 웰보른
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벤 씨. 카덴헤드
엑손 케미칼 패턴츠, 인코포레이티드
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    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
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    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

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  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

An olefin polymerization supported catalyst comprising the supported reaction product of at least one metallocene of a metal of Group IVB, VB, and VIB of the Periodic Table, a non-metallocene transition metal containing compound of a Group IVB, VB, or VIB metal and an alumoxane, said reaction product formed in the presence of the support. The supported product is highly useful for the polymerization of olefins especially ethylene and especially for the copolymerization of ethylene and other mono and diolefins.

Description

신규한 지지 중합촉매New Supported Polymerization Catalyst

본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음Since this is an open matter, no full text was included.

Claims (15)

주가율표의 IVB 및 VIB족 금속의 최소한 하나의 메탈로센, IVB, VB 및 VIB족 금속의 최소한 하나의 비-메탈로센 전이금속 화합물 및 알루옥산의, 지지체 존재하에 형성된, 지지된 반응생성물을 포함하는 올레핀 중합지지촉매.Supported reaction products formed in the presence of a support of at least one metallocene of Group IVB and Group VIB metals, at least one non-metallocene transition metal compound of Group IVB, VB and Group VIB metals and aluoxane Olefin polymerization support catalyst comprising. 제1항에 있어서, 지지체가 IIA, IIIA, IVB 또는 IVB족 원소의 다공성 무기산화물인 올레핀 중합지지촉매.The olefin polymerization support catalyst according to claim 1, wherein the support is a porous inorganic oxide of an IIA, IIIA, IVB or IVB element. 제1항 또는 제2항에 있어서, 지지체가실리카인 올레핀 중합지지촉매.The olefin polymerization support catalyst according to claim 1 or 2, wherein the support is silica. 제1항 내지 제3항중 어느 한 항에 있어서, 메탈로센이 티타늄, 지르코늄, 하프늄 및 바나듐 메탈로센, 및 이들 둘이상의 혼합물로부터 선택된 올레핀 중합지지촉매.The olefin polymerization support catalyst according to any one of claims 1 to 3, wherein the metallocene is selected from titanium, zirconium, hafnium and vanadium metallocene, and mixtures of two or more thereof. 제1항 내지 제4항중 어느 한 항에 있어서, 비-메탈로센 전이금속 화합물이 티타늄 테트라클로라이드, 바나듐 테트라클로라이드, 바나듐 옥시트리클로라이드 및 이들 둘이상의 혼합물로부터 선택된 올레핀 중합지지촉매.The olefin polymerization support catalyst according to any one of claims 1 to 4, wherein the non-metallocene transition metal compound is selected from titanium tetrachloride, vanadium tetrachloride, vanadium oxytrichloride and mixtures of two or more thereof. 제1항 내지 제5항중 어느 한 항에 있어서, 알룸옥산이 메틸 알룸옥산인 올레핀 중합지지촉매.The olefin polymerization support catalyst according to any one of claims 1 to 5, wherein the alumoxane is methyl alumoxane. 제1항 내지 제6항중 어느 한 항에 있어서, 지지된 생성물 내의알루미늄 대 전이금속 몰비가 1 : 1 내지 300 : 1의 범위내에 있는 올레핀 중합지지촉매.The olefin polymerization support catalyst according to any one of claims 1 to 6, wherein the molar ratio of aluminum to transition metal in the supported product is in the range of 1: 1 to 300: 1. 제7항에 있어서, 몰비가 50 : 1 내지 5 : 1의 범위내에 있는 올레핀 중합지지촉매.8. The olefin polymerization support catalyst according to claim 7, wherein the molar ratio is in the range of 50: 1 to 5: 1. 제1항 내지 제8항중 어느 한 항에 있어서, 메탈로센이 다음 일반식(Ⅰ)(Ⅱ) 및 (Ⅲ)으로 표시되고, 비-메탈로센 전이금속 화합물이 TrX'4-q(OR1)q, TrX'4-qR2 q, VOX'3및 VO(OR1)3으로 표시되는 올레핀 중합지지촉매.The metallocene of claim 1, wherein the metallocene is represented by the following general formulas (I) (II) and (III), wherein the non-metallocene transition metal compound is TrX ′ 4-q (OR 1 ) An olefin polymerization support catalyst represented by q , TrX ' 4-q R 2 q , VOX' 3 and VO (OR 1 ) 3 . (C5R'k)gR"s(C5R'k)MQ3-g(Ⅱ)(C 5 R'k ) g R " s (C 5 R'k ) MQ 3-g (II) R"s(C5R'k)2MQ(Ⅲ)R " s (C 5 R ' k ) 2 MQ (III) 상기식에서, Cp는사이클로펜타디에닐 환이고 ; M은 4b, 5b 또는 6b족 전이금속이고 ; R은 탄소수 1 내지 20의 하이드로카빌그룹 또는 하이드로 카복시그룹이고 ; X는 할로겐이고 ; m은 1 내지 3, n은 0 내지 3, q는 0 내지 3이며 m+n+q의 합은 M의 산화상태와 같고 단, 일반식 TrX'4-q(OR1)q및 TrX'4-qR2 q에서 q는 0q4 이며 ; (C5R'5)m사이클로펜타디에닐 또는 치환된 사이클로펜타디에닐이며 ; R'는 각각 같거나 다르며, 수소, 또는 탄소수 1 내지 20의 알킬, 알케닐, 아릴, 알킬아릴 및 아릴알킬로부터 선택된 하이드로 카빌라디칼 이거나, 2개의탄소원작 함께 결합하여 C4내지 C6환을 형성하고 ; R"는 두(C5R'k)환을 연결하는 C1-C4알킬렌 라디칼, 디알킬 게르마늄 또는 실리콘, 또는 알킬 포스핀 또는 아민라디칼이고 ; Q는 탄소수 1 내지 20의 아릴, 알킬 알케닐, 알킬아릴 및 아릴 알킬 라디칼로부터 선택된 하이드로 카빌라디칼, 탄소수 1 내지 20의 하이드로카복시라디칼 또는 할로겐이며 이들은 각각 같거나 다를 수 있고 ; Q'는 탄소수 1 내지 20의 알킬리덴 라디칼이고 ; s는 0 또는 1 이고 ; g는 0.1 또는 2이고 ; s는 g가 0일 때 0이고 ; k는 s가 1일 때 4이며, s가 0일 때 5이고 ; Tr은 IVB, VB 또는 VIB족 금속이고 ; X'는 할로겐이고 ; R1은 탄소수 1 내지 20의 알킬, 아릴 또는 사이클로알킬그룹이고 ; R2는 탄소수 1 내지 20의 알킬, 아릴, 아르알킬 또는 치환된 아르알킬그룹이다.Wherein Cp is a cyclopentadienyl ring; M is a 4b, 5b or 6b group transition metal; R is a hydrocarbyl group or hydrocarboxy group having 1 to 20 carbon atoms; X is halogen; m is 1 to 3, n is 0 to 3, q is 0 to 3 and the sum of m + n + q is equal to the oxidation state of M, except that the general formulas TrX ' 4-q (OR 1 ) q and TrX' 4 in -q R q 2 q is 0 q 4; (C 5 R′5) m cyclopentadienyl or substituted cyclopentadienyl; Each R 'is the same or different and is hydrogen or a hydrocarbyradical selected from alkyl, alkenyl, aryl, alkylaryl and arylalkyl having 1 to 20 carbon atoms, or two carbon atoms are joined together to form a C 4 to C 6 ring and ; R ″ is a C 1 -C 4 alkylene radical, dialkyl germanium or silicon, or an alkyl phosphine or amine radical connecting two (C 5 R ′ k ) rings; Q is an aryl, alkyl al having from 1 to 20 carbon atoms Hydrocarby radicals selected from kenyl, alkylaryl and aryl alkyl radicals, hydrocarboxy radicals or halogens of 1 to 20 carbon atoms, which may each be the same or different; Q 'is an alkylidene radical of 1 to 20 carbon atoms; s is 0 or 1, g is 0.1 or 2, s is 0 when g is 0, k is 4 when s is 1, 5 when s is 0, Tr is IVB, VB or VIB metal; X Is halogen; R 1 is an alkyl, aryl or cycloalkyl group having 1 to 20 carbon atoms; R 2 is an alkyl, aryl, aralkyl or substituted aralkyl group having 1 to 20 carbon atoms. 제9항에 있어서, 메탈로센이 비스(사이클로펜타디에닐) 지르코늄 디클로라이드, 비스(사이클로펜타디에닐) 지르코늄 메틸 클로라이드, 비스(사이클로펜타디에닐) 지르코늄 디메틸, 비스(메틸사이클로펜타디에닐) 비르코늄 디클로라이드, 비스(메틸사이클로펜타디에닐) 지르코늄 메틸 클로라이드, 비스(메틸사이클로펜타디에닐) 지르코늄 메틸, 비스(펜타메틸사이클로펜타디에닐) 지르코늄 디클로라이드, 비스(펜타메틸사이클로펜타디에닐) 지르코늄 메틸 클로라이드, 비스(펜탈메틸사이클로펜타디에닐) 지르코늄 디메틸, 비스(n-부틸-사이클로펜타디에닐) 지르코늄 디클로라이드, 비스(n-부틸-사이클로펜타디에닐) 지르코늄 메틸 클로라이드, 비스(n-부틸-사이클로펜타디에닐) 지르코늄 디메틸, 비스(사이클로펜타디에닐) 티타늄 디페닐, 비스(사이클로펜타디에닐) 티타늄 디클로라이드, 비스(사이클로펜타디에닐) 티타늄 메틸 클로라이드, 비스(사이클로펜타디에닐) 티타늄 디메틸, 비스(메틸사이클로펜타디에닐) 티타늄 디페닐, 비스(메틸사이클로펜타디에닐) 티타늄 디클로라이드, 비스(메틸사이클로펜타디에닐) 티타늄 디페닐, 비스(메틸사이클로펜타디에닐) 티타늄 메틸 클로라이드, 비스(메틸사이클로펜타디에닐) 티타늄 디메틸, 비스(펜타메틸사이클로펜타디에닐) 티타늄 디클로라이드, 비스(펜타메틸사이클로펜타디에닐) 티타늄 디페닐, 비스(펜타메틸사이클로펜타디에닐) 티타늄 메틸클로라이드, 비스(펜타메틸사이클로펜타디에닐) 티타늄 디메틸, 비스(n-부틸-사이클로펜타디에닐) 티타늄 디페닐, 비스(n-부틸-사이클로펜타디에닐) 티타늄 디클로라이드 및 이들 혼합물로부터 선택되고, 비-메탈로센 화합물은 티타늄 테트라클로라이드, 바나듐 테트라클로라이드 ac 바나듐 옥시트리클로라이드로부터 선택된 올레핀 중합지지촉매.The metallocene of claim 9, wherein the metallocene is bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium methyl chloride, bis (cyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) Birconium dichloride, bis (methylcyclopentadienyl) zirconium methyl chloride, bis (methylcyclopentadienyl) zirconium methyl, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) Zirconium methyl chloride, bis (pentalmethylcyclopentadienyl) zirconium dimethyl, bis (n-butyl-cyclopentadienyl) zirconium dichloride, bis (n-butyl-cyclopentadienyl) zirconium methyl chloride, bis (n- Butyl-cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclo Pentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium methyl chloride, bis (cyclopentadienyl) titanium dimethyl, bis (methylcyclopentadienyl) titanium diphenyl, bis (methylcyclopentadienyl) titanium Dichloride, bis (methylcyclopentadienyl) titanium diphenyl, bis (methylcyclopentadienyl) titanium methyl chloride, bis (methylcyclopentadienyl) titanium dimethyl, bis (pentamethylcyclopentadienyl) titanium dichloride , Bis (pentamethylcyclopentadienyl) titanium diphenyl, bis (pentamethylcyclopentadienyl) titanium methyl chloride, bis (pentamethylcyclopentadienyl) titanium dimethyl, bis (n-butyl-cyclopentadienyl) Titanium diphenyl, bis (n-butyl-cyclopentadienyl) titanium dichloride and mixtures thereof; The talocene compound is an olefin polymerization support catalyst selected from titanium tetrachloride, vanadium tetrachloride ac vanadium oxytrichloride. 최소한 하나의 메탈로센과 최소한 하나의 비-메탈로센 화합물을 불활성 탄화수소용매중의 지지체 슬러리와 불활성 탄화수소용매중의 알룸옥산에 첨가함을 특징으로 하는, 제1항에 정의돈 올레핀 중합지지촉매의 제조방법.At least one metallocene and at least one non-metallocene compound are added to a support slurry in an inert hydrocarbon solvent and to alumoxane in an inert hydrocarbon solvent. Manufacturing method. 제11항에 있어서, 알루미늄과 금속을 기준으로 알룸옥산 대 메탈로센의 몰비가 300 : 1 내지 1 : 1의 범위내에 있고, 메탈로센화합물 대 1-메탈로센 전이금속화합물의 몰비가 비-메탈로센 전이금속화합물 몰당 메탈로센 100 내지 0.01몰의 범위내에 있음을 특징으로 하는 방법.The molar ratio of alumoxane to metallocene based on aluminum and metal is in the range of 300: 1 to 1: 1, and the molar ratio of metallocene compound to 1-metallocene transition metal compound is 12. -Metallocene transition metal compound in the range of 100 to 0.01 moles of metallocene per mole. 제1항 내지 제10항중 어느 한 항에 따른 지지촉매와 유기금속 보조촉매를 포함함을 특징으로 하는 올레핀 중합용 촉매계.A catalyst system for olefin polymerization, comprising a support catalyst according to any one of claims 1 to 10 and an organometallic cocatalyst. 제13항에 있어서, 보조촉매가 알루미늄 알킬화합물을 포함함을 특징으로 하는 촉매계.The catalyst system according to claim 13, wherein the cocatalyst comprises an aluminum alkyl compound. 단량체를 제1항 내지 제10항중 어느 한 항에 따른 지지촉매, 제11항 또는 제12항에 따른 방법에 의해 제조된 지지촉매 또는 제13항 또는 제14항에 따른 촉매계의 존재하에 중합시킴을 특징으로 하는, 에틸렌 중합체, 또는 에틸렌과 알파-올레핀 또는 디올레핀의 공중합체를 제조하는 방법.The monomers are polymerized in the presence of a support catalyst according to any one of claims 1 to 10, a support catalyst prepared by the method according to claim 11 or a catalyst system according to claim 13 or 14. Characterized in that an ethylene polymer or copolymer of ethylene and an alpha-olefin or diolefin is produced. ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
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Families Citing this family (273)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5153157A (en) † 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
DE3751694T2 (en) * 1987-04-03 1996-08-01 Fina Technology Metallocene catalyst systems for the polymerization of olefins, with a silicon-hydrocarbyl bridge.
DE3726067A1 (en) 1987-08-06 1989-02-16 Hoechst Ag METHOD FOR PRODUCING 1-OLEFIN POLYMERS
AU603487B2 (en) * 1987-09-14 1990-11-15 Exxon Chemical Patents Inc. Method for preparing an active metallocene-alumoxane catalyst in situ during polymerization
DE3808267A1 (en) * 1988-03-12 1989-09-21 Hoechst Ag METHOD FOR PRODUCING 1-OLEFIN POLYMERS
US5008228A (en) * 1988-03-29 1991-04-16 Exxon Chemical Patents Inc. Method for preparing a silica gel supported metallocene-alumoxane catalyst
NO172242C (en) * 1988-04-26 1993-06-23 Showa Denko Kk PROCEDURE FOR PREPARING ETHYLENE POLYMERS
US4871705A (en) * 1988-06-16 1989-10-03 Exxon Chemical Patents Inc. Process for production of a high molecular weight ethylene a-olefin elastomer with a metallocene alumoxane catalyst
US6025448A (en) 1989-08-31 2000-02-15 The Dow Chemical Company Gas phase polymerization of olefins
EP0436328A3 (en) * 1989-12-13 1992-09-16 Mitsui Toatsu Chemicals, Inc. Method for polymerizing alpha-olefin
US5032562A (en) * 1989-12-27 1991-07-16 Mobil Oil Corporation Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution
US5120696A (en) * 1989-12-29 1992-06-09 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst and process for the polymerization of olefins
US6538080B1 (en) 1990-07-03 2003-03-25 Bp Chemicals Limited Gas phase polymerization of olefins
US5369196A (en) † 1990-11-30 1994-11-29 Idemitsu Kosan Co., Ltd. Production process of olefin based polymers
CA2069995C (en) * 1991-05-31 1996-04-09 Mitsui Chemicals, Incorporated Olefin polymerization solid catalyst, olefin polymerization catalyst and olefin polymerization
GB9116297D0 (en) * 1991-07-29 1991-09-11 Shell Int Research Co-oligomerisation process
US5847053A (en) * 1991-10-15 1998-12-08 The Dow Chemical Company Ethylene polymer film made from ethylene polymer blends
AU656033B2 (en) * 1991-10-28 1995-01-19 Shell Internationale Research Maatschappij B.V. Group IVA metal compounds and catalyst compositions based thereon
DE69224600T2 (en) * 1991-11-12 1998-08-27 Nippon Oil Co Ltd Catalyst components for olefin polymerization
US5362824A (en) * 1991-12-13 1994-11-08 Mobil Oil Corporation Olefin polymerization catalysts
US5461017A (en) * 1991-12-13 1995-10-24 Mobil Oil Corporation Olefin polymerization catalysts
US6043401A (en) * 1992-05-26 2000-03-28 Bp Amoco Corporation Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture
US5688887A (en) * 1992-05-26 1997-11-18 Amoco Corporation Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture
DE69328955T2 (en) * 1992-09-04 2000-11-09 Bp Chem Int Ltd Catalyst compositions and processes for making polyolefins
EP0587440A3 (en) * 1992-09-10 1995-03-08 Nippon Oil Co Ltd Catalyst component for the polymerisation of olefins and process for preparing olefin polymers using same.
US5260245A (en) * 1992-10-19 1993-11-09 Mobil Oil Corporation High activity polyethylene catalysts
US5420220A (en) * 1993-03-25 1995-05-30 Mobil Oil Corporation LLDPE films
US5332706A (en) * 1992-12-28 1994-07-26 Mobil Oil Corporation Process and a catalyst for preventing reactor fouling
US5602067A (en) * 1992-12-28 1997-02-11 Mobil Oil Corporation Process and a catalyst for preventing reactor fouling
KR100301978B1 (en) * 1993-01-29 2001-11-14 리챠드 지. 워터맨 Ethylene Copolymerization
BE1006880A3 (en) * 1993-03-01 1995-01-17 Solvay Precurseur solid system of a catalyst for olefin polymerization, method of preparation, catalytic system including the solid precursor and method for polymerization of olefins in the presence of this system catalyst.
US6228449B1 (en) 1994-01-31 2001-05-08 3M Innovative Properties Company Sheet material
US5523136A (en) * 1993-04-30 1996-06-04 Cypress Packaging Packaging film, packages and methods for using them
IT1264680B1 (en) 1993-07-07 1996-10-04 Spherilene Srl SUPPORTED CATALYSTS FOR THE POLYMERIZATION OF OLEFINS
CA2125999C (en) 1993-07-12 1998-09-22 Paul Nick Georgelos Puncture resistant heat shrinkable film containing narrow molecular weight ethylene alpha olefin
US5397613A (en) * 1993-07-12 1995-03-14 Viskase Corporation Puncture resistant heat shrinkable film containing narrow molecular weight ethylene alpha olefin
US5401816A (en) * 1993-09-27 1995-03-28 Phillips Petroleum Company Transition metal catalyst, method of preparing catalyst, polymerization process employing catalyst, and polymer produced
US5466649A (en) * 1993-10-15 1995-11-14 Exxon Chemical Patents Inc. Polymerization catalyst systems, their production and use
ES2155095T5 (en) * 1993-10-21 2006-04-16 Exxonmobil Oil Corporation MIXTURES OF POLYOLEFINS WITH BIMODAL DISTRIBUTION OF MOLECULAR PESOS.
US5397757A (en) * 1993-10-27 1995-03-14 Mobil Oil Corporation Cocatalysts for metallocene-based olefin polymerization catalyst systems
US5614456A (en) * 1993-11-15 1997-03-25 Mobil Oil Corporation Catalyst for bimodal molecular weight distribution ethylene polymers and copolymers
DE69415829T2 (en) * 1993-11-18 1999-05-20 Mobil Oil Corp CATALYST COMPOSITION FOR THE COPOLYMERIZATION OF ETHYLENE
WO1995013872A1 (en) * 1993-11-18 1995-05-26 Mobil Oil Corporation Catalyst for preparing alpha-olefin polymers and copolymers
US6245705B1 (en) * 1993-11-18 2001-06-12 Univation Technologies Cocatalysts for metallocene-based olefin polymerization catalyst systems
DE4344672C1 (en) * 1993-12-27 1995-06-14 Basf Ag Process for the preparation of polymers of ethylene by suspension polymerization
US5416179A (en) * 1994-03-16 1995-05-16 Phillips Petroleum Company Catalyst compositions and olefin polymerization
US5648438A (en) * 1994-04-01 1997-07-15 Exxon Chemical Patents, Inc. Process for producing polymers with multimodal molecular weight distributions
US5460861A (en) * 1994-05-10 1995-10-24 Viskase Corporation Multilayer stretch/shrink film
IT1270070B (en) * 1994-07-08 1997-04-28 Spherilene Srl COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE
JP3349277B2 (en) * 1994-07-26 2002-11-20 新日本石油株式会社 Method for producing polyolefin
JPH10505622A (en) 1994-09-08 1998-06-02 モービル・オイル・コーポレーション Catalytic control of wide / 2 mode MWD resin in a single reactor
US5525678A (en) * 1994-09-22 1996-06-11 Mobil Oil Corporation Process for controlling the MWD of a broad/bimodal resin produced in a single reactor
US5773106A (en) 1994-10-21 1998-06-30 The Dow Chemical Company Polyolefin compositions exhibiting heat resistivity, low hexane-extractives and controlled modulus
US5529965A (en) * 1994-10-28 1996-06-25 Exxon Chemical Patents Inc. Polymerization catalyst systems, their production and use
US6506866B2 (en) * 1994-11-17 2003-01-14 Dow Global Technologies Inc. Ethylene copolymer compositions
US6043180A (en) * 1994-11-17 2000-03-28 The Dow Chemical Company Supported catalyst component, supported catalyst, their preparation, and addition polymerization process
US5539056A (en) * 1995-01-31 1996-07-23 Exxon Chemical Patents Inc. Thermoplastic elastomers
US5516848A (en) * 1995-01-31 1996-05-14 Exxon Chemical Patents Inc. Process to produce thermoplastic elastomers
US5882750A (en) * 1995-07-03 1999-03-16 Mobil Oil Corporation Single reactor bimodal HMW-HDPE film resin with improved bubble stability
EP0756931B2 (en) * 1995-07-31 2011-06-22 Kureha Corporation Multilayer film
US5869575A (en) * 1995-08-02 1999-02-09 The Dow Chemical Company Ethylene interpolymerizations
ES2120868B1 (en) * 1995-08-03 2000-09-16 Repsol Quimica Sa METALOGEN TYPE HETEREOGENEOUS CATALYST SYSTEM, FOR PROCESSES OF OBTAINING POLYOLEFINS.
US5916982A (en) * 1995-09-29 1999-06-29 Nippon Oil Co., Ltd. Process for the production of polyolefins
US6486089B1 (en) 1995-11-09 2002-11-26 Exxonmobil Oil Corporation Bimetallic catalyst for ethylene polymerization reactions with uniform component distribution
US6395669B1 (en) 1996-01-18 2002-05-28 Equistar Chemicals, Lp Catalyst component and system
US5814399A (en) * 1996-03-12 1998-09-29 Tenneco Packaging Stretch wrap films
US5749202A (en) * 1996-03-12 1998-05-12 Tenneco Packaging Stretch wrap films
US5998017A (en) * 1996-03-12 1999-12-07 Tenneco Packaging Stretch wrap films
USRE38429E1 (en) * 1996-03-12 2004-02-17 Tyco Plastics Services Ag Stretch wrap films
US5976682A (en) * 1996-03-12 1999-11-02 Tenneco Packaging Stretch wrap films
US5902684A (en) * 1996-03-12 1999-05-11 Tenneco Packaging Inc. Multilayered Metallocene stretch wrap films
US5752362A (en) * 1996-03-12 1998-05-19 Tenneco Packaging Stretch wrap films
US6417130B1 (en) 1996-03-25 2002-07-09 Exxonmobil Oil Corporation One pot preparation of bimetallic catalysts for ethylene 1-olefin copolymerization
ES2129323B1 (en) * 1996-04-18 2000-09-16 Repsol Quimica Sa PROCEDURE FOR OBTAINING A CATALYTIC SYSTEM FOR THE POLYMERIZATION OF ALPHA-OLEFINS IN SUSPENSION IN GAS PHASE AT LOW AND HIGH TEMPERATURES OR IN MASS AT HIGH PRESSURES AND HIGH OR LOW TEMPERATURES
JP2000514493A (en) * 1996-07-15 2000-10-31 モービル・オイル・コーポレーション Comonomer pretreatment bimetallic catalysts for blow molding and film applications
ES2154017T3 (en) 1996-10-31 2001-03-16 Repsol Quimica Sa CATALYTIC SYSTEMS FOR THE POLYMERIZATION AND COPOLYMERIZATION OF ALFA-OLEFINS.
US5851070A (en) * 1996-12-05 1998-12-22 Tenneco Packaging Inc. Seals for plastic bags
US5919535A (en) 1996-12-05 1999-07-06 Tenneco Packaging Fins for plastic bags
US6376035B1 (en) 1996-12-05 2002-04-23 Pactiv Corporation Zipper fins for plastic bags
EP0853091A1 (en) * 1997-01-13 1998-07-15 Bp Chemicals S.N.C. Polymerisation process
US5989725A (en) * 1997-01-16 1999-11-23 Tenneco Packaging Clear high molecular weight film
GB9700945D0 (en) * 1997-01-17 1997-03-05 Bp Chem Int Ltd Catalyst activators
ES2249539T3 (en) * 1997-01-30 2006-04-01 Total Petrochemicals Research Feluy SELECTIVE ACTIVITY OF METALOCENE TYPE CATALYST FOR PRODUCTION OF ISOTACTIC POLY-ALFA-OLEFINS.
EP0856524A1 (en) 1997-02-01 1998-08-05 Repsol Quimica S.A. Heterogeneous catalyst components for olefins polymerization, preparation process and use thereof
US6013378A (en) * 1997-03-17 2000-01-11 Tenneco Packaging HMW HDPE film with improved impact strength
US6093480A (en) * 1997-05-21 2000-07-25 Tenneco Packaging Stretch wrap films
US5907942A (en) * 1997-05-21 1999-06-01 Tenneco Packaging Stretch wrap films
US5922441A (en) * 1997-06-11 1999-07-13 Tenneco Packaging Inc. Stretch wrap films
US5907943A (en) * 1997-06-11 1999-06-01 Tenneco Packaging Inc. Stretch wrap films
US6268447B1 (en) 1998-12-18 2001-07-31 Univation Technologies, L.L.C. Olefin polymerization catalyst
US6103657A (en) 1997-07-02 2000-08-15 Union Carbide Chemicals & Plastics Technology Corporation Catalyst for the production of olefin polymers
CA2210131C (en) * 1997-07-09 2005-08-02 Douglas W. Stephan Supported phosphinimine-cp catalysts
US6051525A (en) * 1997-07-14 2000-04-18 Mobil Corporation Catalyst for the manufacture of polyethylene with a broad or bimodal molecular weight distribution
US6153551A (en) 1997-07-14 2000-11-28 Mobil Oil Corporation Preparation of supported catalyst using trialkylaluminum-metallocene contact products
WO1999007785A1 (en) 1997-08-08 1999-02-18 The Dow Chemical Company Sheet materials suitable for use as a floor, wall or ceiling covering material, and processes and intermediates for making the same
DE69807708T2 (en) 1997-08-27 2003-01-02 Dow Chemical Co ELASTOMERS WITH IMPROVED PROCESSABILITY
US6083611A (en) * 1997-11-12 2000-07-04 Tenneco Packaging, Inc. Roll wrap film
US6124412A (en) * 1997-12-29 2000-09-26 Saudi Basic Industries Corporation Alumoxane-enhanced, supported ziegler-natta polymerization catalysts, methods of making same, processes of using same and polymers produced therefrom
US6569964B2 (en) 1997-12-29 2003-05-27 Saudi Basic Industries Corporation Alumoxane-enhanced, supported Ziegler-Natta catalysts, methods of making same, processes of using same and polymers produced therefrom
DE69914012T2 (en) 1998-04-27 2004-12-09 Repsol Quimica S.A. Catalyst systems for the polymerization and copolymerization of alpha olefins
US6245868B1 (en) 1998-05-29 2001-06-12 Univation Technologies Catalyst delivery method, a catalyst feeder and their use in a polymerization process
US6136747A (en) * 1998-06-19 2000-10-24 Union Carbide Chemicals & Plastics Technology Corporation Mixed catalyst composition for the production of olefin polymers
US6303719B1 (en) 1998-12-18 2001-10-16 Univation Technologies Olefin polymerization catalyst system
US6258903B1 (en) 1998-12-18 2001-07-10 Univation Technologies Mixed catalyst system
US6653254B1 (en) * 1999-02-22 2003-11-25 Fina Technology, Inc Ziegler-Natta catalyst with metallocene for olefin polymerization
CA2278042C (en) 1999-07-19 2008-12-16 Nova Chemicals Corporation Mixed phosphinimine catalyst
US6403520B1 (en) 1999-09-17 2002-06-11 Saudi Basic Industries Corporation Catalyst compositions for polymerizing olefins to multimodal molecular weight distribution polymer, processes for production and use of the catalyst
US6548442B1 (en) * 1999-12-03 2003-04-15 Phillips Petroleum Company Organometal compound catalyst
US6444605B1 (en) 1999-12-28 2002-09-03 Union Carbide Chemicals & Plastics Technology Corporation Mixed metal alkoxide and cycloalkadienyl catalysts for the production of polyolefins
US6399531B1 (en) 1999-12-28 2002-06-04 Union Carbide Chemicals & Plastics Technology Corporation Hybrid ziegler-natta and cycloalkadienyl catalysts for the production of polyolefins
GC0000293A (en) * 2000-10-10 2006-11-01 Saudi Basic Ind Corp Catalyst composition and process for olfin polymerization and copolymerization using supported metallocene catalyst systems
AU2002246517A1 (en) * 2001-01-16 2002-08-12 Exxonmobil Chemical Patents Inc. Catalysts with at least two transition metal compounds and polymerization processes using them
CA2447769C (en) * 2001-06-13 2011-07-26 Energy & Environmental International, L.C. Bulk polymerization reactors and methods for polymerization
CN1691979A (en) * 2001-11-30 2005-11-02 埃克森美孚化学专利公司 Bimetallic catalysts with higher activity
AU2002332129A1 (en) * 2001-11-30 2003-06-17 Exxonmobil Chemical Patents, Inc. Ethylene/alpha-olefin copolymer made with a non-single-site/single-site catalyst combination, its preparation and use
EP1461151A4 (en) * 2001-11-30 2010-03-24 Univation Tech Llc Method of making mixed ziegler-natta/metallocene catalysts
ES2321806T3 (en) 2001-12-19 2009-06-12 Borealis Technology Oy PRODUCTION OF SUPPORTED CATALYSTS FOR OLEFIN POLYMERIZATION.
EP1323747A1 (en) 2001-12-19 2003-07-02 Borealis Technology Oy Production of olefin polymerisation catalysts
BR0309539A (en) * 2002-05-06 2005-03-01 Union Carbide Chem Plastic Mixed catalyst compositions for the production of polyolefins and their use
US20040052690A1 (en) * 2002-09-12 2004-03-18 Eaton Gerald B. Polymerization reactant injection system
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
EP1620479B1 (en) 2002-10-15 2013-07-24 ExxonMobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
KR20050084349A (en) * 2002-12-17 2005-08-26 비피 케미칼즈 리미티드 Supported olefin polymerization catalyst
RU2339650C2 (en) 2003-03-21 2008-11-27 Дау Глобал Текнолоджиз, Инк. Method for olefin polymerisation with adjustable morphology
US6953764B2 (en) 2003-05-02 2005-10-11 Dow Global Technologies Inc. High activity olefin polymerization catalyst and process
EP1489110B1 (en) 2003-06-20 2012-01-18 Borealis Polymers Oy Method for preparing an olefin polymerisation catalyst composition
CN100351014C (en) * 2004-07-29 2007-11-28 中国石油化工股份有限公司 Non-metallocene catalyst, and preparation method
GB0423555D0 (en) 2004-10-22 2004-11-24 Borealis Tech Oy Process
KR101075404B1 (en) 2004-12-17 2011-10-24 양지 페트로케미컬 컴퍼니 코., 리미티드. Supported non-metallocene olefin polymerization catalyst, preparation and use thereof
CN101133092B (en) * 2005-03-04 2011-01-12 尤尼威蒂恩技术有限公司 Ziegler-type catalysts having increased productivity
CN101305044B (en) 2005-10-21 2011-12-21 保瑞利斯科技公司 Composition
EP1795542A1 (en) 2005-12-07 2007-06-13 Borealis Technology Oy Polymer
ES2588577T3 (en) 2005-12-30 2016-11-03 Borealis Technology Oy Catalyst particles
EP1803747A1 (en) 2005-12-30 2007-07-04 Borealis Technology Oy Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films
US7683002B2 (en) * 2006-04-04 2010-03-23 Fina Technology, Inc. Transition metal catalyst and formation thereof
US20070299222A1 (en) * 2006-04-04 2007-12-27 Fina Technology, Inc. Transition metal catalysts and formation thereof
EP1878764B2 (en) 2006-07-14 2015-04-22 Borealis Technology Oy High density polyethylene
WO2008047173A1 (en) * 2006-10-19 2008-04-24 Centro De Investigacion En Quimica Aplicada Catalyst for the heterogeneous phase polymerisation of conjugated dienes and olefins, method for obtaining same and use thereof
US7662894B2 (en) * 2006-12-19 2010-02-16 Saudi Bosic Industries Corporation Polymer supported metallocene catalyst composition for polymerizing olefins
DE602007005452D1 (en) 2007-01-22 2010-05-06 Borealis Tech Oy Polypropylene composition with low surface energy
CA2605044C (en) * 2007-10-01 2014-12-02 Nova Chemicals Corporation Polymerization process using a mixed catalyst system
EP2202246B1 (en) 2007-10-16 2016-06-15 Sinopec Yangzi Petrochemical Company Ltd. Non-metallocene catalyst supported on magnesium compound and its preparation method
WO2009052700A1 (en) 2007-10-16 2009-04-30 Sinopec Yangzi Petrochemical Company Ltd. Supported non-metallocene catalyst and its preparation method
TW200932762A (en) 2007-10-22 2009-08-01 Univation Tech Llc Polyethylene compositions having improved properties
US20100280206A1 (en) 2007-11-09 2010-11-04 Borealis Technology Oy Polyethylene copolymer
TW200936619A (en) 2007-11-15 2009-09-01 Univation Tech Llc Polymerization catalysts, methods of making, methods of using, and polyolefin products made therefrom
WO2011087520A1 (en) 2009-12-22 2011-07-21 Univation Technologies, Llc Catalyst systems having a tailored hydrogen response
EP2130860A1 (en) 2008-06-06 2009-12-09 Borealis Technology Oy Polymer
EP2133389A1 (en) 2008-06-12 2009-12-16 Borealis AG Polypropylene composition
EP2172490A1 (en) 2008-10-03 2010-04-07 Ineos Europe Limited Controlled polymerisation process
WO2010052264A1 (en) 2008-11-07 2010-05-14 Borealis Ag Solid catalyst composition
EP2186832B1 (en) 2008-11-10 2012-09-12 Borealis AG Process for the preparation of an unsupported, solid metallocene catalyst system and its use in polymerization of olefins
EP2186831B1 (en) 2008-11-10 2013-01-02 Borealis AG Process for the preparation of an unsupported, solid olefin polymerisation catalyst and use in polymerisation of olefins
WO2010071798A1 (en) 2008-12-18 2010-06-24 Univation Technologies, Llc Method for seed bed treatment for a polymerization reaction
EP2204410A1 (en) 2008-12-31 2010-07-07 Borealis AG Article coated with a composition comprising polyethylene prepared with a single site catalyst
CN102414228B (en) 2009-05-14 2014-05-07 尤尼威蒂恩技术有限责任公司 Mixed metal catalyst systems having a tailored hydrogen response
EP2275476A1 (en) 2009-06-09 2011-01-19 Borealis AG Automotive material with excellent flow, high stiffness, excellent ductility and low CLTE
SI2308923T1 (en) 2009-10-09 2012-08-31 Borealis Ag Glass fibre composite of improved processability
EP2495261B1 (en) 2009-10-26 2020-08-26 China Petroleum & Chemical Corporation Supported non-metallocene catalyst, manufacturing method and application thereof
CN102712701A (en) 2009-12-07 2012-10-03 尤尼威蒂恩技术有限责任公司 Methods for reducing static charge of a catalyst and methods for using the catalyst to produce polyolefins
EP2330136B1 (en) 2009-12-07 2013-08-28 Borealis AG Process for the preparation of an unsupported, solid metallocene catalyst system and its use in polymerization of olefins
CN102652142B (en) * 2009-12-16 2014-05-28 巴塞尔聚烯烃股份有限公司 Polymerization process in the presence of an antistatic agent
US8829128B2 (en) 2009-12-22 2014-09-09 Borealis Ag Preparation of polypropylene in the presence of a single-site catalyst
ES2535323T3 (en) 2009-12-22 2015-05-08 Borealis Ag Preparation of single site catalysts
EP2338920A1 (en) 2009-12-22 2011-06-29 Borealis AG Preparation of single-site catalysts
EP2357035A1 (en) 2010-01-13 2011-08-17 Ineos Europe Limited Polymer powder storage and/or transport and/or degassing vessels
EP2383298A1 (en) 2010-04-30 2011-11-02 Ineos Europe Limited Polymerization process
EP2383301A1 (en) 2010-04-30 2011-11-02 Ineos Europe Limited Polymerization process
EP2738183A1 (en) 2010-05-07 2014-06-04 Borealis AG Preparation of a solid catalyst system
ES2564189T3 (en) 2010-05-07 2016-03-18 Borealis Ag Preparation of a solid catalyst system
EP2385073A1 (en) 2010-05-07 2011-11-09 Borealis AG Process for the preparation of a solid metallocene catalyst system and its use in polymerisation of olefins
EP2386583A1 (en) 2010-05-07 2011-11-16 Borealis AG Process for the preparation of a solid metallocene catalyst system and its use in polymerisation of olefins
EP2415598B1 (en) 2010-08-06 2014-02-26 Borealis AG Multilayer film
EP2632980B1 (en) 2010-10-28 2018-05-16 Borealis AG Single site polymer
US9394381B2 (en) 2010-11-29 2016-07-19 Ineos Sales (Uk) Limited Polymerisation control process
EP2495264B1 (en) 2011-03-04 2013-05-08 Borealis AG Exterior automotive article with reduced paintability failure
ES2462544T3 (en) 2011-08-03 2014-05-23 Borealis Ag Movie
US8383740B1 (en) 2011-08-12 2013-02-26 Ineos Usa Llc Horizontal agitator
EP2748210A4 (en) * 2011-08-25 2015-03-25 Hanwha Chemical Corp A process for the preparation of polyethylene wax using metallocene catalyst
CN102964474B (en) * 2011-08-31 2015-01-14 中国石油化工股份有限公司 Supported non-metallocene catalyst, preparation method and application
CN102964479B (en) * 2011-08-31 2015-01-14 中国石油化工股份有限公司 Supported non-metallocene catalyst, preparation method and application
CN102964488B (en) * 2011-08-31 2015-01-14 中国石油化工股份有限公司 Supported non-metallocene catalyst, preparation method and application
CN102964473A (en) * 2011-08-31 2013-03-13 中国石油化工股份有限公司 Supported non-metallocene catalyst, preparation method and application
ES2665545T3 (en) 2011-10-17 2018-04-26 Ineos Europe Ag Control of the polymer degassing process
KR101331556B1 (en) 2012-03-30 2013-11-20 대림산업 주식회사 Multimodal polyolefin resin and article prepared with the same
EP2834301B1 (en) 2012-04-04 2016-09-14 Borealis AG High-flow fiber reinforced polypropylene composition
EP2722346A1 (en) 2012-10-18 2014-04-23 Borealis AG Polymerisation process and catalyst
ES2622627T3 (en) 2012-10-18 2017-07-06 Borealis Ag Polymerization procedure
EP2722345B1 (en) 2012-10-18 2018-12-05 Borealis AG Catalyst for the polymerisation of olefins
KR101437509B1 (en) 2012-12-03 2014-09-03 대림산업 주식회사 Catalyst composition for preparing multimodal polyolefin resin having superior moldability and mechanical properties and polymerization method using the same
CN104918947A (en) 2012-12-28 2015-09-16 尤尼威蒂恩技术有限责任公司 Methods for integrating aluminoxane production into catalyst production
EP2829558B1 (en) 2013-07-24 2016-12-14 Borealis AG Process
ES2607378T3 (en) 2013-07-24 2017-03-31 Borealis Ag Process
US9670347B2 (en) 2013-08-14 2017-06-06 Borealis Ag Propylene composition with improved impact resistance at low temperature
EP3036284B1 (en) 2013-08-21 2018-12-26 Borealis AG High flow polyolefin composition with high stiffness and toughness
CN105452363B (en) 2013-08-21 2018-06-12 博里利斯股份公司 High flowing polyolefin composition with high rigidity and toughness
PT2853563T (en) 2013-09-27 2016-07-14 Borealis Ag Films suitable for bopp processing from polymers with high xs and high tm
ES2568615T3 (en) 2013-10-11 2016-05-03 Borealis Ag Label film oriented in the machine direction
ES2661108T3 (en) 2013-10-24 2018-03-27 Borealis Ag Low melting polypropylene homopolymer with high regioerror content and high molecular weight
EP2865713B1 (en) 2013-10-24 2016-04-20 Borealis AG Blow molded article based on bimodal random copolymer
CN105722869B (en) 2013-10-29 2017-09-12 北欧化工公司 Solid single-point catalyst with high polymerization activity
BR112016009549B1 (en) 2013-11-22 2021-07-27 Borealis Ag LOW EMISSION PROPYLENE HOMOPOLYMER WITH HIGH FLUIDITY INDEX
US9828698B2 (en) 2013-12-04 2017-11-28 Borealis Ag Phthalate-free PP homopolymers for meltblown fibers
US9637602B2 (en) 2013-12-18 2017-05-02 Borealis Ag BOPP film with improved stiffness/toughness balance
WO2015107020A1 (en) 2014-01-17 2015-07-23 Borealis Ag Process for preparing propylene/1-butene copolymers
EP3102635B1 (en) 2014-02-06 2020-10-07 Borealis AG Soft copolymers with high impact strength
PL3102634T3 (en) 2014-02-06 2020-11-16 Borealis Ag Soft and transparent impact copolymers
EP2907841A1 (en) 2014-02-14 2015-08-19 Borealis AG Polypropylene composite
CN106164104A (en) 2014-04-02 2016-11-23 尤尼威蒂恩技术有限责任公司 Continuity composition and preparation and application thereof
ES2659731T3 (en) 2014-05-20 2018-03-19 Borealis Ag Polypropylene composition for automotive interior applications
EP2995631A1 (en) 2014-09-12 2016-03-16 Borealis AG Process for producing graft copolymers on polyolefin backbone
US9796795B2 (en) 2015-01-14 2017-10-24 Exxonmobil Chemical Patents Inc. Tetrahydroindacenyl catalyst composition, catalyst system, and processes for use thereof
WO2016135213A1 (en) 2015-02-27 2016-09-01 Borealis Ag Laminated film structure based on polyethylene only
SG11201707037TA (en) 2015-03-10 2017-09-28 Univation Tech Llc Spray dried catalyst compositions, methods for preparation and use in olefin polymerization processes
EP3286231B1 (en) 2015-04-20 2019-10-09 ExxonMobil Chemical Patents Inc. Catalyst composition comprising fluorided support and processes for use thereof
US10618989B2 (en) 2015-04-20 2020-04-14 Exxonmobil Chemical Patents Inc. Polyethylene composition
US10640583B2 (en) 2015-04-20 2020-05-05 Exxonmobil Chemical Patents, Inc. Catalyst composition comprising fluorided support and processes for use thereof
US10533063B2 (en) 2015-04-20 2020-01-14 Exxonmobil Chemical Patents Inc. Supported catalyst systems and processes for use thereof
EP3288984B1 (en) 2015-04-27 2023-08-09 Univation Technologies, LLC Supported catalyst compositions having improved flow properties and preparation thereof
FI3320004T4 (en) 2015-07-08 2024-01-26 Chevron Phillips Chemical Co Lp Ziegler-natta-metallocene dual catalyst systems with activator-supports
US9845367B2 (en) 2015-09-24 2017-12-19 Chevron Phillips Chemical Company Lp Heterogeneous Ziegler-Natta catalysts with fluorided silica-coated alumina
US9540457B1 (en) 2015-09-24 2017-01-10 Chevron Phillips Chemical Company Lp Ziegler-natta—metallocene dual catalyst systems with activator-supports
US9758599B2 (en) 2015-09-24 2017-09-12 Chevron Phillips Chemical Company Lp Heterogeneous Ziegler-Natta catalysts with fluorided silica-coated alumina
WO2017102704A1 (en) 2015-12-15 2017-06-22 Borealis Ag Polyethylene based laminated film structure with barrier properties
KR101800866B1 (en) 2016-04-26 2017-12-21 대림산업 주식회사 Multimodal polyolefin resin with high melt strength and article prepared with the same
EP3241611B1 (en) 2016-05-02 2020-03-04 Borealis AG A process for feeding a polymerisation catalyst
US9803037B1 (en) 2016-05-03 2017-10-31 Exxonmobil Chemical Patents Inc. Tetrahydro-as-indacenyl catalyst composition, catalyst system, and processes for use thereof
CN109312015B (en) 2016-05-03 2021-10-26 埃克森美孚化学专利公司 Tetrahydroindacenyl catalyst compositions, catalyst systems, and methods of use thereof
CN109153225A (en) 2016-06-03 2019-01-04 博里利斯股份公司 Multilayered structure
EP3261096A1 (en) 2016-06-21 2017-12-27 Borealis AG Cable and composition
EP3261095A1 (en) 2016-06-21 2017-12-27 Borealis AG Cable with improved electrical properties
CN109328211A (en) 2016-06-21 2019-02-12 博里利斯股份公司 The polymer composition for electric wire and cable application with advantageous thermomechanical property and electrical characteristic
EP3261093B1 (en) 2016-06-21 2023-08-02 Borealis AG Cable with advantageous electrical properties
WO2017220724A1 (en) 2016-06-23 2017-12-28 Borealis Ag Process for catalyst deactivation
WO2018091653A1 (en) 2016-11-18 2018-05-24 Borealis Ag Catalyst
WO2018151903A1 (en) 2017-02-20 2018-08-23 Exxonmobil Chemical Patents Inc. Supported catalyst systems and processes for use thereof
US10723819B2 (en) 2017-02-20 2020-07-28 Exxonmobil Chemical Patents, Inc. Supported catalyst systems and processes for use thereof
US10844150B2 (en) 2017-08-04 2020-11-24 Exxonmobil Chemical Patents Inc. Mixed catalysts with 2,6-bis(imino)pyridyl iron complexes and bridged hafnocenes
CN111108130B (en) 2017-08-04 2022-06-28 埃克森美孚化学专利公司 Has the advantages ofcontaining-CH2-SiMe3Hybrid catalysts of partially unbridged hafnocenes
US10703838B2 (en) 2017-10-31 2020-07-07 Exxonmobil Chemical Patents Inc. Mixed catalyst systems with four metallocenes on a single support
US10926250B2 (en) 2017-12-01 2021-02-23 Exxonmobil Chemical Patents Inc. Catalyst systems and polymerization processes for using the same
CN115850552A (en) 2017-12-01 2023-03-28 埃克森美孚化学专利公司 Catalyst system and polymerization process using the same
BR112020010518B1 (en) 2017-12-18 2023-11-28 Dow Global Technologies Llc Method for making a polyethylene composition
US11384170B2 (en) 2017-12-21 2022-07-12 Borealis Ag Process for the preparation of solid catalyst
US10865258B2 (en) 2018-01-31 2020-12-15 Exxonmobil Chemical Patents Inc. Mixed catalyst systems containing bridged metallocenes with a pendant group 13 element, processes for making a polymer product using same, and products made from same
US10851187B2 (en) 2018-01-31 2020-12-01 Exxonmobil Chemical Patents Inc. Bridged metallocene catalysts with a pendant group 13 element, catalyst systems containing same, processes for making a polymer product using same, and products made from same
US10899853B2 (en) 2018-03-19 2021-01-26 Exxonmobil Chemical Patents Inc. Processes for producing high propylene content PEDM using tetrahydroindacenyl catalyst systems
WO2019194957A1 (en) 2018-04-06 2019-10-10 Exxonmobil Chemcial Patents Inc. Compatibilized thermoplastic vulcanizate compositions
BR112021003478A2 (en) 2018-09-26 2021-05-18 Borealis Ag Propylene random copolymer for use in film applications
WO2020064314A1 (en) 2018-09-26 2020-04-02 Borealis Ag Propylene copolymer with excellent optical properties
WO2020064190A1 (en) 2018-09-26 2020-04-02 Borealis Ag Propylene copolymer composition with excellent optical and mechanical properties
CN113056508B (en) 2018-11-23 2023-08-04 博里利斯股份公司 Polypropylene composition with improved optical properties and anti-whitening properties
EP3887406A1 (en) 2018-11-30 2021-10-06 Borealis AG Washing process
ES2945963T3 (en) 2018-12-14 2023-07-11 Borealis Ag Polypropylene composition with favorable combination of optics, softness and low sealing
EP3999564A1 (en) 2019-07-17 2022-05-25 ExxonMobil Chemical Patents Inc. Pressure sensitive adhesives comprising propylene-ethylene(-diene) copolymers
JP2022543558A (en) * 2019-07-31 2022-10-13 ダウ グローバル テクノロジーズ エルエルシー Polymerization catalyst for producing polyethylene with high molecular weight
JP2022542254A (en) * 2019-07-31 2022-09-30 ダウ グローバル テクノロジーズ エルエルシー Polymerization of Ethylene in a Solution Process Using Ziegler-Natta and Hydrogenation Catalysts
US11472828B2 (en) 2019-10-11 2022-10-18 Exxonmobil Chemical Patents Inc. Indacene based metallocene catalysts useful in the production of propylene polymers
EP3825357A1 (en) 2019-11-25 2021-05-26 Borealis AG Propylene composition for foaming with improved mechanical properties
WO2022129409A1 (en) 2020-12-18 2022-06-23 Borealis Ag Modification of polyethylene terpolymer
EP4019582A1 (en) 2020-12-23 2022-06-29 Borealis AG Polyethylene film
CN116685638A (en) 2021-01-08 2023-09-01 博里利斯股份公司 Composition and method for producing the same
EP4277936A1 (en) 2021-01-12 2023-11-22 ExxonMobil Chemical Patents Inc. Asymmetric constrained geometry catalysts
EP4036130B1 (en) 2021-01-29 2023-03-22 Borealis AG Modification of polyethylene copolymer
EP4053194B1 (en) 2021-03-03 2023-08-02 Borealis AG Monolayer blown film
EP4056598B1 (en) 2021-03-09 2023-09-13 Borealis AG Polyethylene composition for a film layer
ES2963967T3 (en) 2021-03-09 2024-04-03 Borealis Ag Polyethylene composition for one layer of film
EP4305075A1 (en) 2021-03-09 2024-01-17 Borealis AG Polyethylene composition for a film layer
EP4163332A1 (en) 2021-10-10 2023-04-12 Borealis AG Polyethylene composition for a film layer
EP4166581A1 (en) 2021-10-12 2023-04-19 Borealis AG Propylene composition for foaming with high melt flow rate
WO2023198579A1 (en) 2022-04-11 2023-10-19 Borealis Ag Multilayer film
EP4389776A1 (en) 2022-12-20 2024-06-26 Borealis AG Process
EP4389783A1 (en) 2022-12-20 2024-06-26 Borealis AG Catalyst transition process

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3135809A (en) * 1960-07-21 1964-06-02 Southern Res Inst Isomerization process
US3231550A (en) * 1964-06-04 1966-01-25 Union Carbide Corp Olefin polymerization
JPS4948475B1 (en) * 1970-08-11 1974-12-21
DE2608863A1 (en) * 1976-03-04 1977-09-08 Basf Ag Ethylene polymerisation using Ziegler catalyst system - contg. bis-cyclopentadienyl-titanium di-alkyl cpd., aluminium tri-alkyl cpd. and water
DE2608933A1 (en) * 1976-03-04 1977-09-08 Basf Ag Ethylene polymerisation using Ziegler catalyst system - contg. cyclopentadienyl zirconium cpd., aluminium tri-alkyl cpd. and opt. water
US4210559A (en) * 1978-10-30 1980-07-01 Standard Oil Company (Indiana) Catalyst for the preparation of polyalpha-olefins having broad molecular weight distributions
DE3007725A1 (en) * 1980-02-29 1981-09-17 Hansjörg Prof. Dr. 2000 Hamburg Sinn METHOD FOR PRODUCING POLYETHYLENE, POLYPROPYLENE AND COPOLYMERS
CA1168212A (en) * 1981-01-31 1984-05-29 Alexander Johnstone Polymerisation catalyst
US4530914A (en) * 1983-06-06 1985-07-23 Exxon Research & Engineering Co. Process and catalyst for producing polyethylene having a broad molecular weight distribution
ZA844157B (en) * 1983-06-06 1986-01-29 Exxon Research Engineering Co Process and catalyst for polyolefin density and molecular weight control
CA1268754A (en) * 1985-06-21 1990-05-08 Howard Curtis Welborn, Jr. Supported polymerization catalyst
US4701432A (en) * 1985-11-15 1987-10-20 Exxon Chemical Patents Inc. Supported polymerization catalyst
JPH0780930B2 (en) * 1985-12-26 1995-08-30 三井石油化学工業株式会社 Method for polymerizing α-olefin
US4659685A (en) * 1986-03-17 1987-04-21 The Dow Chemical Company Heterogeneous organometallic catalysts containing a supported titanium compound and at least one other supported organometallic compound
JPH01188619A (en) * 1988-01-21 1989-07-27 Nkk Corp Method for rh vacuum degasification

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CA1300119C (en) 1992-05-05
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AU7916587A (en) 1988-04-07
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EP0260130A1 (en) 1988-03-16
WO1988002008A1 (en) 1988-03-24
FI891109A0 (en) 1989-03-08
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US5183867A (en) 1993-02-02
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ZA876545B (en) 1988-03-02
YU166987A (en) 1989-04-30
DK254988D0 (en) 1988-05-09
MX169193B (en) 1993-06-24
IL83708A0 (en) 1988-01-31
DE3788096T2 (en) 1994-03-17
US5077255A (en) 1991-12-31
ATE97139T1 (en) 1993-11-15
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YU10289A (en) 1990-04-30

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